Chemical mechanical polishing pad and method of making same

ABSTRACT

A chemical mechanical polishing pad is provided, comprising: a chemical mechanical polishing layer having a polishing surface; wherein the chemical mechanical polishing layer is formed by combining (a) a poly side (P) liquid component, comprising: an amine-carbon dioxide adduct; and, at least one of a polyol, a polyamine and a alcohol amine; and (b) an iso side (I) liquid component, comprising: polyfunctional isocyanate; wherein the chemical mechanical polishing layer has a porosity of &gt;10 vol %; wherein the chemical mechanical polishing layer has a Shore D hardness of &lt;40; and, wherein the polishing surface is adapted for polishing a substrate. Methods of making and using the same are also provided.

This application is a continuation-in-part of U.S. Ser. No. 14/751,340,filed Jun. 26, 2015, now pending.

The present invention relates to a chemical mechanical polishing padhaving a polishing layer. More particularly, the present inventionrelates to a chemical mechanical polishing pad having a chemicalmechanical polishing layer having a polishing surface; wherein thechemical mechanical polishing layer is formed by combining (a) a polyside (P) liquid component, comprising: an amine-carbon dioxide adduct;and, at least one of a polyol, a polyamine and a alcohol amine; and (b)an iso side (I) liquid component, comprising: polyfunctional isocyanate;wherein the chemical mechanical polishing layer has a porosity of ≧10vol %; wherein the chemical mechanical polishing layer has a Shore Dhardness of <40; and, wherein the polishing surface is adapted forpolishing a substrate; and, to methods of making and using the same.

In the fabrication of integrated circuits and other electronic devices,multiple layers of conducting, semiconducting and dielectric materialsare deposited onto and removed from a surface of a semiconductor wafer.Thin layers of conducting, semiconducting and dielectric materials maybe deposited using a number of deposition techniques. Common depositiontechniques in modern wafer processing include physical vapor deposition(PVD), also known as sputtering, chemical vapor deposition (CVD),plasma-enhanced chemical vapor deposition (PECVD) and electrochemicalplating, among others. Common removal techniques include wet and dryisotropic and anisotropic etching, among others.

As layers of materials are sequentially deposited and removed, theuppermost surface of the wafer becomes non-planar. Because subsequentsemiconductor processing (e.g., metallization) requires the wafer tohave a flat surface, the wafer needs to be planarized. Planarization isuseful for removing undesired surface topography and surface defects,such as rough surfaces, agglomerated materials, crystal lattice damage,scratches and contaminated layers or materials.

Chemical mechanical planarization, or chemical mechanical polishing(CMP), is a common technique used to planarize or polish work piecessuch as semiconductor wafers. In conventional CMP, a wafer carrier, orpolishing head, is mounted on a carrier assembly. The polishing headholds the wafer and positions the wafer in contact with a polishinglayer of a polishing pad that is mounted on a table or platen within aCMP apparatus. The carrier assembly provides a controllable pressurebetween the wafer and polishing pad. Simultaneously, a polishing medium(e.g., slurry) is dispensed onto the polishing pad and is drawn into thegap between the wafer and polishing layer. To effect polishing, thepolishing pad and wafer typically rotate relative to one another. As thepolishing pad rotates beneath the wafer, the wafer sweeps out atypically annular polishing track, or polishing region, wherein thewafer's surface directly confronts the polishing layer. The wafersurface is polished and made planar by chemical and mechanical action ofthe polishing layer and polishing medium on the surface.

Hirose et al. disclose a method of making polishing layers in U.S. Pat.No. 8,314,029. Specifically, Hirose et al. disclose a method formanufacturing a polishing pad containing substantially spherical cellsand having high thickness accuracy, which includes preparing a celldispersed urethane composition by a mechanical foaming method;continuously discharging the cell dispersed urethane composition from asingle discharge port to a substantially central portion in the widthdirection of a face material A, while feeding the face material A;laminating a face material B on the cell dispersed urethane composition;then uniformly adjusting the thickness of the cell dispersed urethanecomposition by thickness adjusting means; curing the cell dispersedurethane composition with the thickness adjusted in the preceding stepwithout applying any additional load to the composition so that apolishing sheet including a polyurethane foam is formed; and cutting thepolishing sheet.

Notwithstanding, there is a continuing need for improved chemicalmechanical polishing pads containing chemical mechanical polishinglayers with improved polishing performance.

The present invention provides a chemical mechanical polishing pad,comprising: a chemical mechanical polishing layer having a polishingsurface, a base surface and an average polishing layer thickness,T_(P-avg), measured normal to the polishing surface from the basesurface to the polishing surface; wherein the chemical mechanicalpolishing layer is formed by combining a poly side (P) liquid componentand an iso side (I) liquid component; wherein the poly side (P) liquidcomponent comprises an amine-carbon dioxide adduct; and, at least one ofa (P) side polyol, a (P) side polyamine and a (P) side alcohol amine;wherein the iso side (I) liquid component, comprising at least one (I)side polyfunctional isocyanate; wherein the chemical mechanicalpolishing layer has a porosity of ≧10 vol %; wherein the chemicalmechanical polishing layer has a Shore D hardness of <40; and, whereinthe polishing surface is adapted for polishing a substrate.

The present invention provides a method of making a chemical mechanicalpolishing layer, comprising: providing a poly side (P) liquid component,comprising an amine-carbon dioxide adduct; and, at least one of a (P)side polyol, a (P) side polyamine and a (P) side alcohol amine;providing a iso side (I) liquid component, comprising at least one atleast one (I) side polyfunctional isocyanate; providing a pressurizedgas; providing an axial mixing device having an internal cylindricalchamber; wherein the internal cylindrical chamber has a closed end, anopen end, an axis of symmetry, at least one (P) side liquid feed portthat opens into the internal cylindrical chamber, at least one (I) sideliquid feed port that opens into the internal cylindrical chamber, andat least one tangential pressurized gas feed port that opens into theinternal cylindrical chamber; wherein the closed end and the open endare perpendicular to the axis of symmetry; wherein the at least one (P)side liquid feed port and the at least one (I) side liquid feed port arearranged along a circumference of the internal cylindrical chamberproximate the closed end; wherein the at least one tangentialpressurized gas feed port is arranged along the circumference of theinternal cylindrical chamber downstream of the at least one (P) sideliquid feed port and the at least one (I) side liquid feed port from theclosed end; wherein the poly side (P) liquid component is introducedinto the internal cylindrical chamber through the at least one (P) sideliquid feed port at a (P) side charge pressure of 6,895 to 27,600 kPa;wherein the iso side (I) liquid component is introduced into theinternal cylindrical chamber through the at least one (I) side liquidfeed port at an (I) side charge pressure of 6,895 to 27,600 kPa; whereina combined mass flow rate of the poly side (P) liquid component and theiso side (I) liquid component to the internal cylindrical chamber is 1to 500 g/s, such as, preferably, from 2 to 40 g/s or, more preferably, 2to 25 g/s; wherein the poly side (P) liquid component, the iso side (I)liquid component and the pressurized gas are intermixed within theinternal cylindrical chamber to form a combination; wherein thepressurized gas is introduced into the internal cylindrical chamberthrough the at least one tangential pressurized gas feed port with asupply pressure of 150 to 1,500 kPa; wherein an inlet velocity into theinternal cylindrical chamber of the pressurized gas is 50 to 600 m/scalculated based on ideal gas conditions at 20° C. and 1 atm pressureor, preferably, 75 to 350 m/s; discharging the combination from the openend of the internal cylindrical chamber toward a target at a velocity of5 to 1,000 m/sec, or, preferably, from 10 to 600 m/sec or, morepreferably, from 15 to 450 m/sec; allowing the combination to solidifyinto a cake; and, deriving the chemical mechanical polishing layer fromthe cake, wherein the chemical mechanical polishing layer has a porosityof ≧10 vol % and a polishing surface adapted for polishing a substrate.

The present invention provides a method of making a chemical mechanicalpolishing layer, comprising: providing a poly side (P) liquid component,comprising an amine-carbon dioxide adduct; and, at least one of a (P)side polyol, a (P) side polyamine and a (P) side alcohol amine;providing a iso side (I) liquid component, comprising at least one atleast one (I) side polyfunctional isocyanate; providing a pressurizedgas; providing an axial mixing device having an internal cylindricalchamber; wherein the internal cylindrical chamber has a closed end, anopen end, an axis of symmetry, at least one (P) side liquid feed portthat opens into the internal cylindrical chamber, at least one (I) sideliquid feed port that opens into the internal cylindrical chamber, andat least one tangential pressurized gas feed port that opens into theinternal cylindrical chamber; wherein the closed end and the open endare perpendicular to the axis of symmetry; wherein the at least one (P)side liquid feed port and the at least one (I) side liquid feed port arearranged along a circumference of the internal cylindrical chamberproximate the closed end; wherein the at least one tangentialpressurized gas feed port is arranged along the circumference of theinternal cylindrical chamber downstream of the at least one (P) sideliquid feed port and the at least one (I) side liquid feed port from theclosed end; wherein the poly side (P) liquid component is introducedinto the internal cylindrical chamber through the at least one (P) sideliquid feed port at a (P) side charge pressure of 6,895 to 27,600 kPa;wherein the iso side (I) liquid component is introduced into theinternal cylindrical chamber through the at least one (I) side liquidfeed port at an (I) side charge pressure of 6,895 to 27,600 kPa; whereina combined mass flow rate of the poly side (P) liquid component and theiso side (I) liquid component to the internal cylindrical chamber is 1to 500 g/s, such as, preferably, from 2 to 40 g/s or, more preferably, 2to 25 g/s; wherein the poly side (P) liquid component, the iso side (I)liquid component and the pressurized gas are intermixed within theinternal cylindrical chamber to form a combination; wherein thepressurized gas is introduced into the internal cylindrical chamberthrough the at least one tangential pressurized gas feed port with asupply pressure of 150 to 1,500 kPa; wherein an inlet velocity into theinternal cylindrical chamber of the pressurized gas is 50 to 600 m/scalculated based on ideal gas conditions at 20° C. and 1 atm pressure,or, preferably, 75 to 350 m/s; discharging the combination from the openend of the internal cylindrical chamber toward a target at a velocity of5 to 1,000 m/sec, or, preferably, from 10 to 600 m/sec or, morepreferably, from 15 to 450 m/sec; allowing the combination to solidifyinto a cake; deriving the chemical mechanical polishing layer from thecake; providing a poly side (P) substance, comprising at least one ofthe (P) side polyol, the (P) side polyamine and the (P) side alcoholamine; providing a iso side (I) substance, comprising at least one (I)side polyfunctional isocyanate; wherein the poly side (P) substance isintroduced into the internal cylindrical chamber through the at leastone (P) side liquid feed port at the (P) side charge pressure of 6,895to 27,600 kPa; wherein the iso side (I) substance is introduced into theinternal cylindrical chamber through the at least one (I) side liquidfeed port at the (I) side charge pressure of 6,895 to 27,600 kPa;wherein a combined mass flow rate of the poly side (P) substance and theiso side (I) substance to the internal cylindrical chamber is 1 to 500g/s, such as, preferably, from 2 to 40 g/s or, more preferably, 2 to 25g/s; wherein the poly side (P) substance, the iso side (I) sidesubstance and the pressurized gas are intermixed within the internalcylindrical chamber to form a mixture; wherein the pressurized gas isintroduced into the internal cylindrical chamber through the at leastone tangential pressurized gas feed port with the supply pressure of 150to 1,500 kPa; wherein the inlet velocity into the internal cylindricalchamber of the pressurized gas is 50 to 600 m/s calculated based onideal gas conditions at 20° C. and 1 atm pressure or, preferably, 75 to350 m/s; discharging the mixture from the open end of the internalcylindrical chamber toward a base surface of the chemical mechanicalpolishing layer at a velocity of 5 to 1,000 m/sec, or, preferably, from10 to 600 m/sec or, more preferably, from 15 to 450 m/sec; allowing themixture to solidify on the base surface of the chemical mechanicalpolishing layer to form a subpad; wherein the subpad is integral withthe chemical mechanical polishing layer; wherein the subpad has a subpadporosity that is different from that of the chemical mechanicalpolishing layer; and, wherein the chemical mechanical polishing layerhas a porosity of >10 vol % and a polishing surface adapted forpolishing a substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a depiction of a perspective view of a mold for use in themethod of the present invention.

FIG. 2 is a depiction of a perspective view of a chemical mechanicalpolishing layer of the present invention.

FIG. 3 is a depiction of a side elevational view of an axial mixingdevice for use in the method of the present invention.

FIG. 4 is a cross sectional view taken along line B-B in FIG. 3.

FIG. 5 is a cross sectional view taken along line C-C in FIG. 3.

FIG. 6 is a depiction of a side elevational view of a chemicalmechanical polishing layer of the present invention.

FIG. 7 is a depiction of a side elevational view showing the elevationof an axial mixing device relative to a chemical mechanical polishinglayer of the present invention formed on a mold having a negative groovepattern.

FIG. 8 is depiction of a side elevational view of a cross section of achemical mechanical polishing pad of the present invention with a subpadthat is integral with the chemical mechanical polishing layer.

FIG. 9 is a depiction of a side elevational view of a cross section of achemical mechanical polishing pad of the present invention with a subpadand a platen adhesive.

DETAILED DESCRIPTION

The chemical mechanical polishing pads of the present invention comprisea chemical mechanical polishing layer formed by combining a unique polyside (P) liquid component and an iso side (I) liquid component; whereinthe poly side (P) liquid component comprises an amine-carbon dioxideadduct; and, at least one of a (P) side polyol, a (P) side polyamine anda (P) side alcohol amine; wherein the iso side (I) liquid component,comprising at least one (I) side polyfunctional isocyanate. It has beensurprisingly found that the incorporation of an amine-carbon dioxideadduct into the soft polishing layer formulations of the presentinvention provides a significant improvement in substrate polishingperformance.

The term “polishing medium” as used herein and in the appended claimsencompasses particle-containing polishing solutions andnon-particle-containing solutions, such as abrasive-free andreactive-liquid polishing solutions.

The term “substantially circular cross section” as used herein and inthe appended claims in reference to a mold cavity (20) means that thelongest radius, r_(c), of the mold cavity (20) projected onto the x-yplane (28) from the mold cavity's central axis, C_(axis), (22) to avertical internal boundary (18) of a surrounding wall (15) is ≦20%longer than the shortest radius, r_(c), of the mold cavity (20)projected onto the x-y plane (28) from the mold cavity's central axis,Caxis, (22) to the vertical internal boundary (18). (See FIG. 1).

The term “mold cavity” as used herein and in the appended claims refersto the volume defined by a base (12) and a vertical internal boundary(18) of a surrounding wall (15). (See FIG. 1).

The term “substantially perpendicular” as used herein and in theappended claims in reference to a first feature (e.g., a horizontalinternal boundary; a vertical internal boundary) relative to a secondfeature (e.g., an axis, an x-y plane) means that the first feature is atan angle of 80 to 100° to the second feature.

The term “essentially perpendicular” as used herein and in the appendedclaims in reference to a first feature (e.g., a horizontal internalboundary; a vertical internal boundary) relative to a second feature(e.g., an axis, an x-y plane) means that the first feature is at anangle of 85 to 95° to the second feature.

The term “average polishing layer thickness, T_(P-avg)” as used hereinand in the appended claims in reference to a chemical mechanicalpolishing layer (90) having a polishing surface (95) means the averageof the polishing layer thickness, T_(P), of the chemical mechanicalpolishing layer (90) measured normal to the polishing surface (95) fromthe polishing surface (95) to the base surface (92) of the chemicalmechanical polishing layer (90). (See FIG. 2).

The term “substantially circular cross section” as used herein and inthe appended claims in reference to a chemical mechanical polishinglayer (90) means that the longest radius, r_(p), of the cross sectionfrom the central axis (98) of the chemical mechanical polishing layer(90) to the outer perimeter (110) of the polishing surface (95) of thechemical mechanical polishing layer (90) is ≦20% longer than theshortest radius, r_(p), of the cross section from the central axis (98)to the outer perimeter (110) of the polishing surface (95). (See FIG.2).

The chemical mechanical polishing layer (90) of the present invention ispreferably adapted for rotation about a central axis (98). (See FIG. 2).Preferably, the polishing surface (95) of the chemical mechanicalpolishing layer (90) is in a plane (99) perpendicular to the centralaxis (98). Preferably, the chemical mechanical polishing layer (90) isadapted for rotation in a plane (99) that is at an angle, γ, of 85 to95° to the central axis (98), preferably, of 90° to the central axis(98). Preferably, the chemical mechanical polishing layer (90) has apolishing surface (95) that has a substantially circular cross sectionperpendicular to the central axis (98). Preferably, the radius, r_(p),of the cross section of the polishing surface (95) perpendicular to thecentral axis (98) varies by ≦20% for the cross section, more preferablyby ≦10% for the cross section.

The term “gel time” as used herein and in the appended claims inreference to a combination of a poly side (P) liquid component and aniso side (I) liquid component formed in an axial mixing device of thepresent invention, means the total cure time for that combinationdetermined using a standard test method according to ASTM D3795-00a(Reapproved 2006) (Standard Test Method for Thermal Flow, Cure, andBehavior Properties of Pourable Thermosetting Materials by TorqueRheometer).

The term “poly(urethane) ” as used herein and in the appended claimsencompasses (a) polyurethanes formed from the reaction of (i)isocyanates and (ii) polyols (including diols); and, (b) poly(urethane)formed from the reaction of (i) isocyanates with (ii) polyols (includingdiols) and (iii) water, amines or a combination of water and amines.

Preferably, the chemical mechanical polishing pad method of the presentinvention, comprises: a chemical mechanical polishing layer (90) havinga polishing surface (95), a base surface (92) and an average polishinglayer thickness, T_(P-avg), measured normal to the polishing surface(95) from the base surface (92) to the polishing surface (95); whereinthe chemical mechanical polishing layer (90) is formed by combining apoly side (P) liquid component and an iso side (I) liquid component;wherein the poly side (P) liquid component comprises an amine-carbondioxide adduct; and, at least one of a (P) side polyol, a (P) sidepolyamine and a (P) side alcohol amine; wherein the iso side (I) liquidcomponent, comprising at least one (I) side polyfunctional isocyanate;wherein the chemical mechanical polishing layer (90) has a porosity of≧10 vol %; wherein the polishing layer (90) has a Shore D hardness of<40 (preferably, ≦35; more preferably, ≦30; most preferably, ≦25); and,wherein the polishing surface (95) is adapted for polishing a substrate.(See FIG. 2).

Preferably, the poly side (P) liquid component comprises an amine-carbondioxide adduct; and, at least one of a (P) side polyol, a (P) sidepolyamine and a (P) side alcohol amine. Preferably, the poly side (P)liquid component contains 0.5 to 7 wt % (preferably, 1 to 5 wt %; morepreferably, 2 to 4 wt %) of an amine-carbon dioxide adduct.

Preferably, the amine-carbon dioxide adduct is obtained by contactingcarbon dioxide with an alkanolamine, wherein the alkanolamine containsone to two ether moieties per molecule. More preferably, theamine-carbon dioxide adduct is obtained by contacting carbon dioxidewith an alkanolamine, wherein the alkanolamine has a formulacorresponding to one of the following:

wherein each R′ is independently selected from a hydrogen, a methylgroup and an ethyl group; wherein each R″ is independently selected froma hydrogen, a methyl group and an ethyl group; wherein n is selectedfrom 1 and 2; wherein n′ is selected from 1 and 2; wherein n+n′<3; andwherein x is selected from 1, 2, 3 and 4; wherein x′ is selected from 1,2, 3 and 4. Preferably, the amine-carbon dioxide adduct is obtained bycontacting carbon dioxide with an alkanolamine, wherein the alkanolamineis a primary amine.

Preferably, the (P) side polyol is selected from the group consisting ofdiols, polyols, polyol diols, copolymers thereof and mixtures thereof.More preferably, the (P) side polyol is selected from the groupconsisting of polyether polyols (e.g., poly(oxytetramethylene) glycol,poly(oxypropylene) glycol and mixtures thereof); polycarbonate polyols;polyester polyols; polycaprolactone polyols; mixtures thereof; and,mixtures thereof with one or more low molecular weight polyols selectedfrom the group consisting of ethylene glycol; 1,2-propylene glycol;1,3-propylene glycol; 1,2-butanediol; 1,3-butanediol;2-methyl-1,3-propanediol; 1,4-butanediol; neopentyl glycol;1,5-pentanediol; 3-methyl-1,5-pentanediol; 1,6-hexanediol; diethyleneglycol; dipropylene glycol; and, tripropylene glycol. Still morepreferably, the at least one (P) side polyol is selected from the groupconsisting of polytetramethylene ether glycol (PTMEG); ester basedpolyols (such as ethylene adipates, butylene adipates); polypropyleneether glycols (PPG); polycaprolactone polyols; copolymers thereof; and,mixtures thereof.

Preferably, the poly side (P) liquid component contains at least one (P)side polyol; wherein the at least one (P) side polyol includes a highmolecular weight polyol having a number average molecular weight, M_(N),of 2,500 to 100,000. More preferably, the high molecular weight polyolused has a number average molecular weight, M_(N), of 5,000 to 50,000(still more preferably 7,500 to 25,000; most preferably 10,000 to12,000).

Preferably, the poly side (P) liquid component contains at least one (P)side polyol; wherein the at least one (P) side polyol includes a highmolecular weight polyol having an average of three to ten hydroxylgroups per molecule. More preferably, the high molecular weight polyolused has an average of four to eight (still more preferably five toseven; most preferably six) hydroxyl groups per molecule.

Examples of commercially available high molecular weight polyols includeSpecflex® polyols, Voranol® polyols and Voralux® polyols (available fromThe Dow Chemical Company); Multranol® Specialty Polyols and Ultracel®Flexible Polyols (available from Bayer MaterialScience LLC); andPluracol® Polyols (available from BASF). A number of preferred highmolecular weight polyols are listed in TABLE 1.

TABLE 1 Number of Hydroxyl OH groups Number High molecular weight polyolper molecule M_(N) (mg KOH/g) Multranol ® 3901 Polyol 3.0 6,000 28Pluracol ® 1385 Polyol 3.0 3,200 50 Pluracol ® 380 Polyol 3.0 6,500 25Pluracol ® 1123 Polyol 3.0 7,000 24 ULTRACEL ® 3000 Polyol 4.0 7,500 30SPECFLEX ® NC630 Polyol 4.2 7,602 31 SPECFLEX ® NC632 Polyol 4.7 8,22532 VORALUX ® HF 505 Polyol 6.0 11,400 30 MULTRANOL ® 9185 Polyol 6.03,366 100 VORANOL ® 4053 Polyol 6.9 12,420 31

Preferably, the poly side (P) liquid component contains: 0.5 to 7 wt %(more preferably, 1 to 5 wt %; most preferably, 2 to 4 wt %) of theamine-carbon dioxide adduct; and, 25 to 95 wt % of the (P) side polyol;wherein the (P) side polyol is a high molecular weight polyether polyol;wherein the high molecular weight polyether polyol has a number averagemolecular weight, MN, of 2,500 to 100,000 (more preferably, 5,000 to50,000; still more preferably, 7,500 to 25,000; most preferably 10,000to 12,000) and an average of 4 to 8 (more preferably, 5 to 7; mostpreferably, 6) hydroxyl groups per molecule. Preferably, the poly (P)side polyol is a mixture of a high molecular weight polyether polyol anda low molecular weight polyol; wherein the high molecular weightpolyether polyol has a number average molecular weight, M_(N), of 2,500to 100,000 (more preferably, 5,000 to 50,000; still more preferably,7,500 to 25,000; most preferably 10,000 to 12,000) and an average of 4to 8 (more preferably, 5 to 7; most preferably, 6) hydroxyl groups permolecule; and, wherein the low molecular weight polyol has a numberaverage molecular weight, M_(N), of ≦200 (more preferably, ≦150; mostpreferably, ≦100). More preferably, the poly (P) side polyol is amixture of 70 to 90 wt % of a high molecular weight polyether polyol and10 to 30 wt % of a low molecular weight polyol; wherein the highmolecular weight polyether polyol has a number average molecular weight,M_(N), of 2,500 to 100,000 (more preferably, 5,000 to 50,000; still morepreferably, 7,500 to 25,000; most preferably 10,000 to 12,000) and anaverage of 4 to 8 (more preferably, 5 to 7; most preferably, 6) hydroxylgroups per molecule; and, wherein the low molecular weight polyol has anumber average molecular weight, M_(N), of ≦200 (more preferably, ≦150;most preferably, ≦100).

Preferably, the (P) side polyamine is selected from the group consistingof diamines and other multifunctional amines. More preferably, the (P)side polyamine is selected from the group consisting of aromaticdiamines and other multifunctional aromatic amines; such as, forexample, 4,4′-methylene-bis-o-chloroaniline (“MbOCA”);4,4′-methylene-bis-(3-chloro-2,6-diethylaniline) (“MCDEA”);dimethylthiotoluenediamine; trimethyleneglycol di-p-aminobenzoate;polytetramethyleneoxide di-p-aminobenzoate; polytetramethyleneoxidemono-p-aminobenzoate; polypropyleneoxide di-p-aminobenzoate;polypropyleneoxide mono-p-aminobenzoate; 1,2-bis(2-aminophenylthio)ethane; 4,4′-methylene-bis-aniline; diethyltoluenediamine;5-tert-butyl-2,4-toluendiamine; 3-tert-butyl-2,6-toluenediamine;5-tert-amyl-2,4-toluenediamine; and 3-tert-amyl-2,6-toluenediamine andchlorotoluenediamine.

Preferably, the (P) side alcohol amine is selected from the groupconsisting amine initiated polyols. More preferably, the (P) sidealcohol amine is selected from the group consisting amine initiatedpolyols containing one to four (still more preferably, two to four; mostpreferably, two) nitrogen atoms per molecule. Preferably, the (P) sidealcohol amine is selected from the group consisting amine initiatedpolyols that have an average of at least three hydroxyl groups permolecule. More preferably, the (P) side alcohol amine is selected fromthe group consisting of amine initiated polyols that have an average ofthree to six (still more preferably, three to five; most preferably,four) hydroxyl groups per molecule. Particularly preferred amineinitiated polyols a number average molecular weight, M_(N), of ≦700(preferably, of 150 to 650; more preferably, of 200 to 500; mostpreferably 250 to 300) and have a hydroxyl number (as determined by ASTMTest Method D4274-11) of 350 to 1,200 mg KOH/g. More preferably, theamine initiated polyol used has a hydroxyl number of 400 to 1,000 mgKOH/g (most preferably 600 to 850 mg KOH/g). Examples of commerciallyavailable amine initiated polyols include the Voranol® family of amineinitiated polyols (available from The Dow Chemical Company); theQuadrol® Specialty Polyols (N,N,N′,N′-tetrakis(2-hydroxypropyl ethylenediamine)) (available from BASF); Pluracol® amine based polyols(available from BASF); Multranol® amine based polyols (available fromBayer MaterialScience LLC); triisopropanolamine (TIPA) (available fromThe Dow Chemical Company); and, triethanolamine (TEA) (available fromMallinckrodt Baker Inc.). A number of preferred amine initiated polyolsare listed in TABLE 2.

TABLE 2 Number of OH groups Hydroxyl Number Amine initiated polyol permolecule M_(N) (mg KOH/g) Triethanolamine 3 149 1130 Triisopropanolamine3 192 877 MULTRANOL ® 9138 Polyol 3 240 700 MULTRANOL ® 9170 Polyol 3481 350 VORANOL ® 391 Polyol 4 568 391 VORANOL ® 640 Polyol 4 352 638VORANOL ® 800 Polyol 4 280 801 QUADROL ® Polyol 4 292 770 MULTRANOL ®4050 Polyol 4 356 630 MULTRANOL ® 4063 Polyol 4 488 460 MULTRANOL ® 8114Polyol 4 568 395 MULTRANOL ® 8120 Polyol 4 623 360 MULTRANOL ® 9181Polyol 4 291 770 VORANOL ® 202 Polyol 5 590 475

Preferably, the iso side (I) liquid component, comprises at least one(I) side polyfunctional isocyanate. Preferably, the at least one (I)side polyfunctional isocyanate contains two reactive isocyanate groups(i.e., NCO) per molecule.

Preferably, the at least one (I) side polyfunctional isocyanate isselected from the group consisting of an aliphatic polyfunctionalisocyanate, an aromatic polyfunctional isocyanate and a mixture thereof.More preferably, the (I) side polyfunctional isocyanate is adiisocyanate selected from the group consisting of 2,4-toluenediisocyanate; 2,6-toluene diisocyanate; 4,4′-diphenylmethanediisocyanate; naphthalene-1,5-diisocyanate; tolidine diisocyanate;para-phenylene diisocyanate; xylylene diisocyanate; isophoronediisocyanate; hexamethylene diisocyanate; 4,4′-dicyclohexylmethanediisocyanate; cyclohexanediisocyanate; and, mixtures thereof. Still morepreferably, the at least one (I) side polyfunctional isocyanate is anisocyanate terminated urethane prepolymer formed by the reaction of adiisocyanate with a prepolymer polyol.

Preferably, the at least one (I) side polyfunctional isocyanate is anisocyanate-terminated urethane prepolymer; wherein theisocyanate-terminated urethane prepolymer has 2 to 12 wt % unreactedisocyanate (NCO) groups. More preferably, the isocyanate-terminatedurethane prepolymer used in the method of the present invention has 2 to10 wt % (still more preferably 4 to 8 wt %; most preferably 5 to 7 wt %)unreacted isocyanate (NCO) groups.

Preferably, the isocyanate terminated urethane prepolymer used is thereaction product of a diisocyanate with a prepolymer polyol; wherein theprepolymer polyol is selected from the group consisting of diols,polyols, polyol diols, copolymers thereof and mixtures thereof. Morepreferably, the prepolymer polyol is selected from the group consistingof polyether polyols (e.g., poly(oxytetramethylene) glycol,poly(oxypropylene) glycol and mixtures thereof); polycarbonate polyols;polyester polyols; polycaprolactone polyols; mixtures thereof; and,mixtures thereof with one or more low molecular weight polyols selectedfrom the group consisting of ethylene glycol; 1,2-propylene glycol;1,3-propylene glycol; 1,2-butanediol; 1,3-butanediol;2-methyl-1,3-propanediol; 1,4-butanediol; neopentyl glycol;1,5-pentanediol; 3-methyl-1,5-pentanediol; 1,6-hexanediol; diethyleneglycol; dipropylene glycol; and, tripropylene glycol. Still morepreferably, the prepolymer polyol is selected from the group consistingof polytetramethylene ether glycol (PTMEG); ester based polyols (such asethylene adipates, butylene adipates); polypropylene ether glycols(PPG); polycaprolactone polyols; copolymers thereof and, mixturesthereof. Most preferably, the prepolymer polyol is selected from thegroup consisting of PTMEG and PPG.

Preferably, when the prepolymer polyol is PTMEG, the isocyanateterminated urethane prepolymer has an unreacted isocyanate (NCO)concentration of 2 to 10 wt % (more preferably of 4 to 8 wt %; mostpreferably 6 to 7 wt %). Examples of commercially available PTMEG basedisocyanate terminated urethane prepolymers include Imuthane® prepolymers(available from COIM USA, Inc., such as, PET-80A, PET-85A, PET-90A,PET-93A, PET-95A, PET-60D, PET-70D, PET-75D); Adiprene® prepolymers(available from Chemtura, such as, LF 800A, LF 900A, LF 910A, LF 930A,LF 931A, LF 939A, LF 950A, LF 952A, LF 600D, LF 601D, LF 650D, LF 667,LF 700D, LF750D, LF751D, LF752D, LF753D and L325); Andur® prepolymers(available from Anderson Development Company, such as, 70APLF, 80APLF,85APLF, 90APLF, 95APLF, 60DPLF, 70APLF, 75APLF).

Preferably, when the prepolymer polyol is PPG, the isocyanate terminatedurethane prepolymer has an unreacted isocyanate (NCO) concentration of 3to 9 wt % (more preferably 4 to 8 wt %, most preferably 5 to 6 wt %).Examples of commercially available PPG based isocyanate terminatedurethane prepolymers include Imuthane® prepolymers (available from COIMUSA, Inc., such as, PPT-80A, PPT-90A, PPT-95A, PPT-65D, PPT-75D);Adiprene® prepolymers (available from Chemtura, such as, LFG 963A, LFG964A, LFG 740D); and, Andur® prepolymers (available from AndersonDevelopment Company, such as, 8000APLF, 9500APLF, 6500DPLF, 7501DPLF).

Preferably, the isocyanate terminated urethane prepolymer used in themethod of the present invention is a low free isocyanate terminatedurethane prepolymer having less than 0.1 wt % free toluene diisocyanate(TDI) monomer content.

Preferably, the iso side (I) liquid component, comprises at least one(I) side polyfunctional isocyanate; wherein the at least one (I) sidepolyfunctional isocyanate is a non-TDI based isocyanate terminatedurethane prepolymer. Non-TDI based isocyanate terminated urethaneprepolymers can also be used in the method of the present invention. Forexample, isocyanate terminated urethane prepolymers include those formedby the reaction of 4,4′-diphenylmethane diisocyanate (MDI) and polyolssuch as polytetramethylene glycol (PTMEG) with optional diols such as1,4-butanediol (BDO) are acceptable. When such isocyanate terminatedurethane prepolymers are used, the unreacted isocyanate (NCO)concentration is preferably 4 to 10 wt % (more preferably 4 to 8 wt %,most preferably 5 to 7 wt %). Examples of commercially availableisocyanate terminated urethane prepolymers in this category includeImuthane® prepolymers (available from COIM USA, Inc. such as 27-85A,27-90A, 27-95A); Andur® prepolymers (available from Anderson DevelopmentCompany, such as, IE75AP, IE80AP, IE 85AP, IE90AP, IE95AP, IE98AP);Vibrathane® prepolymers (available from Chemtura, such as, B625, B635,B821); Isonate® modified prepolymer (available from The Dow ChemicalCompany, such as, Isonate® 240 with 18.7% NCO, Isonate® 181 with 23%NCO, Isonate® 143L with 29.2% NCO); and, polymeric MDI (available fromThe Dow Chemical Company, such as, PAPI® 20, 27, 94, 95, 580N, 901).

Preferably, at least one of the poly side (P) liquid component and theiso side (I) liquid component can optionally contain additional liquidmaterials. For example, at least one of the poly side (P) liquidcomponent and the iso side (I) liquid component can contain liquidmaterials selected from the group consisting of catalysts (e.g.,tertiary amine catalysts such as Dabco® 33LV catalyst available from AirProducts, Inc.; and tin catalyst such as Fomrez® tin catalyst fromMomentive); and surfactants (e.g., Tegostab® silicon surfactant fromEvonik). Preferably, the poly side (P) liquid component contains anadditional liquid material. More preferably, the poly side (P) liquidcomponent contains an additional liquid material; wherein the additionalliquid material is at least one of a catalyst and a surfactant. Mostpreferably, the poly side (P) liquid component contains a catalyst and asurfactant.

Preferably, the poly side (P) liquid component and the iso side (I)liquid component are provided at a stoichiometric ratio of the reactivehydrogen groups (i.e., the sum of the amine (NH₂) groups and thehydroxyl (OH) groups) in the components of the poly side (P) liquidcomponent to the unreacted isocyanate (NCO) groups in the iso side (I)liquid component of 0.85 to 1.15 (more preferably 0.90 to 1.10; mostpreferably 0.95 to 1.05).

Preferably, the axial mixing device (60) used in the method of making achemical mechanical polishing layer of the present invention has aninternal cylindrical chamber (65). Preferably, the internal cylindricalchamber (65) has a closed end (62) and an open end (68). Preferably, theclosed end (62) and the open end (68) are each substantiallyperpendicular to an axis of symmetry (70) of the internal cylindricalchamber (65). More preferably, the closed end (62) and the open end (68)are each essentially perpendicular to an axis of symmetry (70) of theinternal cylindrical chamber (65). Most preferably, the closed end (62)and the open end (68) are each perpendicular to an axis of symmetry (70)of the internal cylindrical chamber (65). (See FIGS. 3-5).

Preferably, the axial mixing device (60) used in the method of making achemical mechanical polishing layer of the present invention has aninternal cylindrical chamber (65) with an axis of symmetry (70), whereinthe open end (68) has a circular opening (69). More preferably, theaxial mixing device (60) used in the method of the present invention hasan internal cylindrical chamber (65) with an axis of symmetry (70);wherein the open end (68) has a circular opening (69); and, wherein thecircular opening (69) is concentric with the internal cylindricalchamber (65). Most preferably, the axial mixing device (60) used in themethod of the present invention has an internal cylindrical chamber (65)with an axis of symmetry (70); wherein the open end (68) has a circularopening (69); wherein the circular opening (69) is concentric with theinternal cylindrical chamber (65); and, wherein the circular opening(69) is perpendicular to the axis of symmetry (70) of the internalcylindrical chamber (65). Preferably, the circular opening (69) has adiameter of 1 to 10 mm (more preferably, 1.5 to 7.5 mm; still morepreferably 2 to 6 mm; most preferably, 2.5 to 3.5 mm). (See FIGS. 3-5).

Preferably, the axial mixing device (60) used in the method of making achemical mechanical polishing layer the present invention has at leastone (P) side liquid feed port (75) that opens into the internalcylindrical chamber (65). More preferably, the axial mixing device (60)used in the method of the present invention has at least two (P) sideliquid feed ports (75) that open into the internal cylindrical chamber(65). Preferably, when the axial mixing device (60) used in the methodof the present invention has at least two (P) side liquid feed ports(75) that open into the internal cylindrical chamber (65), the at leasttwo (P) side liquid feed ports (75) are arranged evenly about acircumference (67) of the internal cylindrical chamber (65). Morepreferably, when the axial mixing device (60) used in the method of thepresent invention has at least two (P) side liquid feed ports (75) thatopen into the internal cylindrical chamber (65), the at least two (P)side liquid feed ports (75) are arranged evenly about a circumference(67) of the internal cylindrical chamber (65) and are at an equaldistance from the closed end (62) of the internal cylindrical chamber(65). Preferably, the at least one (P) side liquid feed port opens intothe internal cylindrical chamber (65) through an orifice having an innerdiameter of 0.05 to 3 mm (preferably, 0.1 to 0.1 mm; more preferably,0.15 to 0.5 mm). Preferably, the at least one (P) side liquid feed portopens into the internal cylindrical chamber (65) and is directed towardthe axis of symmetry (70) of the internal cylindrical chamber (65). Morepreferably, the at least one (P) side liquid feed port opens into theinternal cylindrical chamber (65) and is directed toward and essentiallyperpendicular to the axis of symmetry (70) of the internal cylindricalchamber (65). Most preferably, the at least one (P) side liquid feedport opens into the internal cylindrical chamber (65) and is directedtoward and perpendicular to the axis of symmetry (70) of the internalcylindrical chamber (65).

Preferably, the axial mixing device (60) used in the method of making achemical mechanical polishing layer of the present invention has atleast one (I) side liquid feed port (80) that opens into the internalcylindrical chamber (65). More preferably, the axial mixing device (60)used in the method of the present invention has at least two (I) sideliquid feed ports (80) that open into the internal cylindrical chamber(65). Preferably, when the axial mixing device (60) used in the methodof the present invention has at least two (I) side liquid feed ports(80) that open into the internal cylindrical chamber (65), the at leasttwo (I) side liquid feed ports (80) are arranged evenly about acircumference (67) of the internal cylindrical chamber (65). Morepreferably, when the axial mixing device (60) used in the method of thepresent invention has at least two (I) side liquid feed ports (80) thatopen into the internal cylindrical chamber (65), the at least two (I)side liquid feed ports (80) are arranged evenly about a circumference(67) of the internal cylindrical chamber (65) and are at an equaldistance from the closed end (62) of the internal cylindrical chamber(65). Preferably, the at least one (I) side liquid feed port opens intothe internal cylindrical chamber (65) through an orifice having an innerdiameter of 0.05 to 3 mm (preferably, 0.1 to 0.1 mm; more preferably,0.15 to 0.5 mm). Preferably, the at least one (I) side liquid feed portopens into the internal cylindrical chamber (65) and is directed towardthe axis of symmetry (70) of the internal cylindrical chamber (65). Morepreferably, the at least one (I) side liquid feed port opens into theinternal cylindrical chamber (65) and is directed toward and essentiallyperpendicular to the axis of symmetry (70) of the internal cylindricalchamber (65). Most preferably, the at least one (I) side liquid feedport opens into the internal cylindrical chamber (65) and is directedtoward and perpendicular to the axis of symmetry (70) of the internalcylindrical chamber (65).

Preferably, the axial mixing device (60) used in the method of making achemical mechanical polishing layer of the present invention has atleast one (P) side liquid feed port (75) that opens into the internalcylindrical chamber (65) and at least one (I) side liquid feed port (80)that opens into the internal cylindrical chamber (65); wherein the atleast one (P) side liquid feed port (75) and the at least one (I) sideliquid feed port (80) are arranged evenly about the circumference (67)of the internal cylindrical chamber (65). More preferably, the axialmixing device (60) used in the method of the present invention has atleast one (P) side liquid feed port (75) that opens into the internalcylindrical chamber (65) and at least one (I) side liquid feed port (80)that opens into the internal cylindrical chamber (65); wherein the atleast one (P) side liquid feed port (75) and the at least one (I) sideliquid feed port (80) are arranged evenly about a circumference (67) ofthe internal cylindrical chamber (65) and are at an equal distance fromthe closed end (62) of the internal cylindrical chamber (65).

Preferably, the axial mixing device (60) used in the method of making achemical mechanical polishing layer of the present invention has atleast two (P) side liquid feed ports (75) that open into the internalcylindrical chamber (65) and at least two (I) side liquid feed ports(80) that open into the internal cylindrical chamber (65). Preferably,when the axial mixing device (60) used in the method of the presentinvention has at least two (P) side liquid feed ports (75) that openinto the internal cylindrical chamber (65) and at least two (I) sideliquid feed ports (80) that open into the internal cylindrical chamber(65), the at least two (P) side liquid feed ports (75) are arrangedevenly about the circumference (67) of the internal cylindrical chamber(65) and the at least two (I) side liquid feed ports (80) are arrangedevenly about the circumference (67) of the internal cylindrical chamber(65). Preferably, when the axial mixing device (60) used in the methodof the present invention has at least two (P) side liquid feed ports(75) that open into the internal cylindrical chamber (65) and at leasttwo (I) side liquid feed ports (80) that open into the internalcylindrical chamber (65), the (P) side liquid feed ports (75) and the(I) side liquid feed ports (80) alternate about the circumference (67)of the internal cylindrical chamber (65). More preferably, when theaxial mixing device (60) used in the method of the present invention hasat least two (P) side liquid feed ports (75) that open into the internalcylindrical chamber (65) and at least two (I) side liquid feed ports(80) that open into the internal cylindrical chamber (65), the (P) sideliquid feed ports (75) and the (I) side liquid feed ports (80) alternateand are evenly spaced about the circumference (67) of the internalcylindrical chamber (65). Most preferably, when the axial mixing device(60) used in the method of the present invention has at least two (P)side liquid feed ports (75) that open into the internal cylindricalchamber (65) and at least two (I) side liquid feed ports (80) that openinto the internal cylindrical chamber (65); the (P) side liquid feedports (75) and the (I) side liquid feed ports (80) alternate and areevenly spaced about the circumference (67) of the internal cylindricalchamber (65); and, the (P) side liquid feed ports (75) and the (I) sideliquid feed ports (80) are all at an equal distance from the closed end(62) of the internal cylindrical chamber (65).

Preferably, the axial mixing device (60) used in the method of making achemical mechanical polishing layer of the present invention has atleast one tangential pressurized gas feed port (85) that opens into theinternal cylindrical chamber (65). More preferably, the axial mixingdevice (60) used in the method of the present invention has at least onetangential pressurized gas feed port (85) that opens into the internalcylindrical chamber (65); wherein the at least one tangentialpressurized gas feed port (85) is arranged along the circumference ofthe internal cylindrical chamber (65) downstream of the at least one (P)side liquid feed port (75) and the at least one (I) side liquid feedport (80) from the closed end (62). Still more preferably, the axialmixing device (60) used in the method of the present invention has atleast two tangential pressurized gas feed ports (85) that open into theinternal cylindrical chamber (65); wherein the at least two tangentialpressurized gas feed ports (85) are arranged along the circumference ofthe internal cylindrical chamber (65) downstream of the at least one (P)side liquid feed port (75) and the at least one (I) side liquid feedport (80) from the closed end (62). Yet still more preferably, the axialmixing device (60) used in the method of the present invention has atleast two tangential pressurized gas feed ports (85) that open into theinternal cylindrical chamber (65); wherein the at least two tangentialpressurized gas feed ports (85) are arranged along the circumference ofthe internal cylindrical chamber (65) downstream of the at least one (P)side liquid feed port (75) and the at least one (I) side liquid feedport (80) from the closed end (62); and, wherein the at least twotangential pressurized gas feed ports (85) are arranged evenly about acircumference (67) of the internal cylindrical chamber (65). Mostpreferably, the axial mixing device (60) used in the method of thepresent invention has at least two tangential pressurized gas feed ports(85) that open into the internal cylindrical chamber (65); wherein theat least two tangential pressurized gas feed ports (85) are arrangedalong the circumference of the internal cylindrical chamber (65)downstream of the at least one (P) side liquid feed port (75) and the atleast one (I) side liquid feed port (80) from the closed end (62); and,wherein the at least two tangential pressurized gas feed ports (85) arearranged evenly about a circumference (67) of the internal cylindricalchamber (65) and are at an equal distance from the closed end (62) ofthe internal cylindrical chamber (65). Preferably, the at least onetangential pressurized gas feed port opens into the internal cylindricalchamber (65) through an orifice having a critical dimension of 0.1 to 5mm (preferably, 0.3 to 3 mm; more preferably, 0.5 to 2 mm). Preferably,the at least one tangential pressurized gas feed port opens into theinternal cylindrical chamber (65) and is directed tangentially along aninternal circumference of the internal cylindrical chamber (65). Morepreferably, the at least one tangential pressurized gas feed port opensinto the internal cylindrical chamber (65) and is directed tangentiallyalong an internal circumference of the internal cylindrical chamber andon a plane that is essentially perpendicular to the axis of symmetry(70) of the internal cylindrical chamber (65). Most preferably, the atleast one tangential pressurized gas feed port opens into the internalcylindrical chamber (65) and is directed tangentially along an internalcircumference of the internal cylindrical chamber and on a plane that isperpendicular to the axis of symmetry (70) of the internal cylindricalchamber (65).

Preferably, the chemical mechanical polishing pad of the presentinvention, comprises a chemical mechanical polishing layer having aShore D hardness of <40 as measured according to ASTM D2240. Morepreferably, the chemical mechanical polishing pad of the presentinvention, comprises a chemical mechanical polishing layer having aShore D hardness of ≦35 (still more preferably, ≦30; most preferably,≦25) as measured according to ASTM D2240.

Preferably, the chemical mechanical polishing pad of the presentinvention, comprises a chemical mechanical polishing layer having aporosity of >10 vol %. More preferably, the chemical mechanicalpolishing pad of the present invention, comprises a chemical mechanicalpolishing layer having a porosity of has a porosity of 25 to 75 vol %(more preferably, 30 to 60 vol %; most preferably, 45 to 55 vol %).

Preferably, the chemical mechanical polishing layer (90) of the presentinvention has an average polishing layer thickness, T_(P-avg), of 20 to150 mils. More preferably the chemical mechanical polishing layer (90)has an average polishing layer thickness, T_(P-avg), of 30 to 125 mils(still more preferably 40 to 120 mils; most preferably 50 to 100 mils).(See FIG. 2).

Preferably, the chemical mechanical polishing layer of the presentinvention is adapted for polishing a substrate; wherein the substrate isat least one of a magnetic substrate, an optical substrate and asemiconductor substrate. More preferably, the chemical mechanicalpolishing layer of the present invention is adapted for polishing asubstrate; wherein the substrate is a semiconductor substrate. Mostpreferably, the chemical mechanical polishing layer of the presentinvention is adapted for polishing a substrate; wherein the substrate isa semiconductor wafer.

Preferably, the chemical mechanical polishing layer of the presentinvention has a polishing surface that has at least one of macrotextureand microtexture to facilitate polishing the substrate. Preferably, thepolishing surface has macrotexture, wherein the macrotexture is designedto do at least one of (i) alleviate at least one of hydroplaning; (ii)influence polishing medium flow; (iii) modify the stiffness of thepolishing layer; (iv) reduce edge effects; and, (v) facilitate thetransfer of polishing debris away from the area between the polishingsurface and the substrate being polished.

Preferably, the chemical mechanical polishing layer of the chemicalmechanical polishing pad of the present invention has at least one of atleast one perforation and at least one groove (105). More preferably,the chemical mechanical polishing layer of the chemical mechanicalpolishing pad of the present invention has at least one groove (105)formed in the polishing layer (90) opening at the polishing surface (95)and having a groove depth, G_(depth), from the polishing surface (95)measured normal to the polishing surface (95) from the polishing surface(95) toward the base surface (92). Preferably, the at least one groove(105) is arranged on the polishing surface (95) such that upon rotationof the chemical mechanical polishing pad during polishing, the at leastone groove (105) sweeps over the substrate. Preferably, the at least onegroove is selected from curved grooves, linear grooves and combinationsthereof. Preferably, the at least one groove has an average groovedepth, G_(depth-avg), of ≧10 mils (preferably, 10 to 150 mils).Preferably, the at least one groove has an average groove depth,G_(depth-avg), <the average polishing layer thickness, T_(P-avg).Preferably, the at least one groove forms a groove pattern thatcomprises at least two grooves having a combination of an average groovedepth, G_(depth-avg), selected from ≧10 mils, ≧15 mils and 15 to 150mils; a width selected from ≧10 mils and 10 to 100 mils; and a pitchselected from ≧30 mils, ≧50 mils, 50 to 200 mils, 70 to 200 mils, and 90to 200 mils. Preferably, the at least one groove is selected from (a) atleast two concentric grooves; (b) at least one spiral groove; (c) across hatch groove pattern; and (d) a combination thereof (See FIG. 6).

Preferably, the groove pattern comprises a plurality of grooves. Morepreferably, the groove pattern is selected from a groove design.Preferably, the groove design is selected from the group consisting ofconcentric grooves (which may be circular or spiral), curved grooves,cross hatch grooves (e.g., arranged as an X-Y grid across the padsurface), other regular designs (e.g., hexagons, triangles), tire treadtype patterns, irregular designs (e.g., fractal patterns), andcombinations thereof. More preferably, the groove design is selectedfrom the group consisting of random grooves, concentric grooves, spiralgrooves, cross-hatched grooves, X-Y grid grooves, hexagonal grooves,triangular grooves, fractal grooves and combinations thereof. Mostpreferably, the polishing surface has a spiral groove pattern formedtherein. The groove profile is preferably selected from rectangular withstraight side walls or the groove cross section may be “V” shaped, “U”shaped, saw-tooth, and combinations thereof.

Preferably, the method of making a chemical mechanical polishing layerof the present invention, comprises: providing a poly side (P) liquidcomponent, comprising an amine-carbon dioxide adduct; and, at least oneof a (P) side polyol, a (P) side polyamine and a (P) side alcohol amine;providing a iso side (I) liquid component, comprising at least one atleast one (I) side polyfunctional isocyanate; providing a pressurizedgas; providing an axial mixing device (60) having an internalcylindrical chamber (65); wherein the internal cylindrical chamber (65)has a closed end (62), an open end (68), an axis of symmetry (70), atleast one (P) side liquid feed port (75) that opens into the internalcylindrical chamber (65), at least one (I) side liquid feed port (80)that opens into the internal cylindrical chamber (65), and at least one(preferably, at least two) tangential pressurized gas feed port (85)that opens into the internal cylindrical chamber (65); wherein theclosed end (62) and the open end (68) are perpendicular to the axis ofsymmetry (70); wherein the at least one (P) side liquid feed port (75)and the at least one (I) side liquid feed port (80) are arranged along acircumference (67) of the internal cylindrical chamber (65) proximatethe closed end (62); wherein the at least one (preferably, at least two)tangential pressurized gas feed port (85) is arranged along thecircumference (67) of the internal cylindrical chamber (65) downstreamof the at least one (P) side liquid feed port (75) and the at least one(I) side liquid feed port (80) from the closed end (62); wherein thepoly side (P) liquid component is introduced into the internalcylindrical chamber (65) through the at least one (P) side liquid feedport (75) at a (P) side charge pressure of 6,895 to 27,600 kPa; whereinthe iso side (I) liquid component is introduced into the internalcylindrical chamber (65) through the at least one (I) side liquid feedport (80) at an (I) side charge pressure of 6,895 to 27,600 kPa; whereina combined mass flow rate of the poly side (P) liquid component and theiso side (I) liquid component to the internal cylindrical chamber is 1to 500 g/s (preferably 2 to 40 g/s; or more preferably, 2 to 25 g/s);wherein the pressurized gas is introduced into the internal cylindricalchamber through the at least one (preferably, at least two) tangentialpressurized gas feed port with a supply pressure of 150 to 1,500 kPa;wherein an inlet velocity into the internal cylindrical chamber of thepressurized gas is 50 to 600 m/s calculated based on ideal gasconditions at 20° C. and 1 atm pressure or, preferably, 75 to 350 m/s;wherein the poly side (P) liquid component, the iso side (I) liquidcomponent and the pressurized gas are intermixed within the internalcylindrical chamber (65) to form a combination; discharging thecombination from the open end (68) of the internal cylindrical chamber(65) toward a target at a velocity of 5 to 1,000 m/sec, or, preferably,from 10 to 600 m/sec or, more preferably, from 15 to 450 m/sec; allowingthe combination to solidify into a cake; and, deriving the chemicalmechanical polishing layer from the cake, wherein the chemicalmechanical polishing layer has a porosity of ≧10 vol % and a polishingsurface adapted for polishing a substrate (preferably, wherein thechemical mechanical polishing layer has a Shore D hardness of <40 (morepreferably, ≦35; more preferably, ≦30; most preferably, ≦25). (See FIGS.3-5).

Preferably, in the method of making a chemical mechanical polishinglayer of the present invention, the poly side (P) liquid component isintroduced into the internal cylindrical chamber (65) through the atleast one (P) side liquid feed port (75) at a (P) side charge pressureof 6,895 to 27,600 kPa. More preferably, the poly side (P) liquidcomponent is introduced into the internal cylindrical chamber (65)through the at least one (P) side liquid feed port (75) at a (P) sidecharge pressure of 8,000 to 20,000 kPa. Most preferably, the poly side(P) liquid component is introduced into the internal cylindrical chamber(65) through the at least one (P) side liquid feed port (75) at a (P)side charge pressure of 10,000 to 17,000 kPa.

Preferably, in the method of making a chemical mechanical polishinglayer of the present invention, the iso side (I) liquid component isintroduced into the internal cylindrical chamber (65) through the atleast one (I) side liquid feed port (80) at an (I) side charge pressureof 6,895 to 27,600 kPa. More preferably, the iso side (I) liquidcomponent is introduced into the internal cylindrical chamber (65)through the at least one (I) side liquid feed port (80) at an (I) sidecharge pressure of 8,000 to 20,000 kPa. Most preferably, the iso side(I) liquid component is introduced into the internal cylindrical chamber(65) through the at least one (I) side liquid feed port (80) at an (I)side charge pressure of 10,000 to 17,000 kPa.

Preferably, in the method of making a chemical mechanical polishinglayer of the present invention, the pressurized gas used is selectedfrom the group consisting of carbon dioxide, nitrogen, air and argon.More preferably, the pressurized gas used is selected from the groupconsisting of carbon dioxide, nitrogen and air. Still more preferably,the pressurized gas used is selected from the group consisting ofnitrogen and air. Most preferably, the pressurized gas used is air.

Preferably, in the method of making a chemical mechanical polishinglayer of the present invention, the pressurized gas used has a watercontent of ≦10 ppm. More preferably, the pressurized gas used has awater content of ≦1 ppm. Still more preferably, the pressurized gas usedhas a water content of ≦0.1 ppm. Most preferably, the pressurized gasused has a water content of ≦0.01 ppm.

Preferably, in the method of making a chemical mechanical polishinglayer of the present invention, the pressurized gas is introduced intothe internal cylindrical chamber (65) though the at least two tangentialpressurized gas feed ports (85) with an inlet velocity, wherein theinlet velocity is 50 to 600 m/s calculated based on ideal gas conditionsat 20° C. and 1 atm pressureor, preferably, 75 to 350 m/s. Withoutwishing to be bound by theory, it is noted that when the inlet velocityis too low, the chemical mechanical polishing layer deposited in themold has an increased likelihood of developing undesirable cracks.

Preferably, in the method of making a chemical mechanical polishinglayer of the present invention, the pressurized gas is introduced intothe internal cylindrical chamber (65) through the at least twotangential pressurized gas feed ports (85) with a supply pressure of 150to 1,500 kPa. More preferably, the pressurized gas is introduced intothe internal cylindrical chamber (65) through the at least twotangential pressurized gas feed ports (85) with a supply pressure of 350to 1,000 kPa. Most preferably, the pressurized gas is introduced intothe internal cylindrical chamber (65) through the at least twotangential pressurized gas feed ports (85) with a supply pressure of 550to 830 kPa.

Preferably, in the method of making a chemical mechanical polishinglayer of the present invention, the combined mass flow rate of the polyside (P) liquid component and the iso side (I) liquid component to theinternal cylindrical chamber (65) is lto 500 g/s (preferably, 2 to 40g/s; or, more preferably, 2 to 25 g/s).

Preferably, in the method of making a chemical mechanical polishinglayer of the present invention, the ratio of (a) the sum of the combinedmass flow rate of the poly side (P) liquid component and the iso side(I) liquid component to the internal cylindrical chamber (65) to (b) themass flow of the pressurized gas to the internal cylindrical chamber(65) (calculated based on ideal gas conditions at 20° C. and 1 atmpressure) is ≦46 to 1 (more preferably, ≦30 to 1).

Preferably, in the method of making a chemical mechanical polishinglayer of the present invention, the combination formed in the axialmixing device (60) is discharged from the open end (68) of the internalcylindrical chamber (65) toward a target (12) at a velocity of 10 to 300m/sec. More preferably, the combination is discharged from the opening(69) at the open end (68) of the axial mixing device (60) with avelocity having a z-component in a direction parallel to the z axis (Z)toward a target (12) of 10 to 300 m/sec. (See FIGS. 1 and 7).

Preferably, in the method of making a chemical mechanical polishinglayer of the present invention, the combination is discharged from theopen end (68) of the axial mixing device (60) at an elevation, E, alongthe z dimension above the target (12). More preferably, the combinationis discharged from the open end (68) of the axial mixing device (60) atan elevation, E, along the z dimension above the target (12); whereinthe average elevation, E_(avg), is 2.5 to 125 cm (more preferably, 7.5to 75 cm; most preferably, 12.5 to 50 cm). (See FIGS. 1 and 7).

Preferably, in the method of making a chemical mechanical polishinglayer of the present invention, the target used is any suitable materialfor receiving the discharged combination. More preferably, the target isa material selected from a plastic surface, a glass surface and a metalsurface. Preferably, the target is selected from flat materials andshaped materials (e.g., a target with a negative groove pattern formedtherein).

Preferably, the target (12) used in the method of the present inventiondefines a negative (14) of a groove pattern; wherein the groove pattern(100) is transferred to the polishing surface (95) of the chemicalmechanical polishing layer (90). Preferably, the target (12) has asubstantially circular cross section having an average radius, r_(c),(preferably, wherein r_(c) is 20 to 100 cm; more preferably, whereinr_(c) is 25 to 65 cm; most preferably, wherein r_(c) is 40 to 60 cm).(See FIGS. 1 and 7).

Preferably, the target (12) used in the method of the present inventionis an integral part of a mold (10) having a surrounding wall (15).Preferably, the surrounding wall defines a vertical internal boundary(18) of the mold cavity (20) that is substantially perpendicular to thex-y plane (28). More preferably, the surrounding wall defines anvertical internal boundary (18) of the mold cavity (20) that isessentially perpendicular to the x-y plane (28). (See FIG. 1).

Preferably, the mold cavity (20) has a central axis, C_(a)ms, (22) thatcoincides with the z-axis and that intersects the horizontal internalboundary (14) of the base (12) of the mold (10) at a center point (21).Preferably, the center point (21) is located at the geometric center ofthe cross section, Cx-sect, (24) of the mold cavity (20) projected ontothe x-y plane (28). (See FIG. 1).

Preferably, the mold cavity's cross section, C_(x-sect), (24) projectedonto the x-y plane (28) can be any regular or irregular two dimensionalshape. Preferably, the mold cavity's cross section, C_(x-sect), (24) isselected from a polygon and an ellipse. More preferably, the moldcavity's cross section, C_(x-sect), (24) is a substantially circularcross section having an average radius, r_(c), (preferably, whereinr_(c) is 20 to 100 cm; more preferably, wherein r_(c) is 25 to 65 cm;most preferably, wherein r_(c) is 40 to 60 cm). Most preferably, themold cavity (20) approximates a right cylindrically shaped region havinga substantially circular cross section, Cx-sect; wherein the mold cavityhas an axis of symmetry, C_(x-sym), (25) which coincides with the moldcavity's central axis, C_(axis), (22); wherein the right cylindricallyshaped region has a cross sectional area, C_(x-area), defined asfollows:

C_(x-area)=πr_(c) ²,

wherein r_(c) is the average radius of the mold cavity's cross sectionalarea, C_(x-area), projected onto the x-y plane (28); and wherein r_(c)is 20 to 100 cm (more preferably, 25 to 65 cm; most preferably, 40 to 60cm). (See FIG. 1).

Preferably, in the method of making a chemical mechanical polishinglayer of the present invention, the combination formed in the axialmixing device has a gel time of 5 to 900 seconds. More preferably, thecombination formed in the axial mixing device has a gel time of 10 to600 seconds. Most preferably, the combination formed in the axial mixingdevice has a gel time of 15 to 120 seconds.

Preferably, the chemical mechanical polishing layer prepared using themethod of the present invention can be interfaced with at least oneadditional layer to form a chemical mechanical polishing pad.Preferably, the chemical mechanical polishing layer prepared using themethod of the present invention is interfaced with a subpad.

Preferably, the method of making a chemical mechanical polishing layer(90) for a chemical mechanical polishing pad (200) of the presentinvention, further comprises: providing a poly side (P) substance,comprising at least one of the (P) side polyol, the (P) side polyamineand the (P) side alcohol amine; providing a iso side (I) substance,comprising at least one (I) side polyfunctional isocyanate; wherein thepoly side (P) substance is introduced into the internal cylindricalchamber through the at least one (P) side liquid feed port at the (P)side charge pressure of 6,895 to 27,600 kPa; wherein the iso side (I)substance is introduced into the internal cylindrical chamber throughthe at least one (I) side liquid feed port at the (I) side chargepressure of 6,895 to 27,600 kPa; wherein a combined mass flow rate ofthe poly side (P) substance and the iso side (I) substance to theinternal cylindrical chamber is 1 to 500 g/s, such as, preferably, from2 to 40 g/s or, more preferably, 2 to 25 g/s; wherein the poly side (P)substance, the iso side (I) side substance and the pressurized gas areintermixed within the internal cylindrical chamber to form a mixture;wherein the pressurized gas is introduced into the internal cylindricalchamber through the at least one tangential pressurized gas feed portwith the supply pressure of 150 to 1,500 kPa; wherein the inlet velocityinto the internal cylindrical chamber of the pressurized gas is 50 to600 m/s calculated based on ideal gas conditions at 20° C. and 1 atmpressure or, preferably, 75 to 350 m/s; discharging the mixture from theopen end of the internal cylindrical chamber toward a base surface ofthe chemical mechanical polishing layer at a velocity of 5 to 1,000m/sec, or, preferably, from 10 to 600 m/sec or, more preferably, from 15to 450 m/sec; allowing the mixture to solidify on the base surface ofthe chemical mechanical polishing layer to form a subpad (220); whereinthe subpad (220) is integral with the chemical mechanical polishinglayer (90); wherein the subpad (220) has a subpad porosity that isdifferent from that of the chemical mechanical polishing layer (90).Preferably, the subpad (220) is adjacent to the base surface (92) of thepolishing layer (90). Preferably, the subpad (220) has a subpadthickness, T_(s), normal to the polishing surface (95) of the chemicalmechanical polishing layer (90). One of ordinary skill in the art willknow to select an appropriate subpad thickness, T_(s), for the subpad(220). Preferably, the subpad (220) has an average subpad thickness,T_(S-avg), of ≧15 mils (more preferably, 30 to 100 mils; most preferably30 to 75 mils). Preferably, the poly side (P) substance and the polyside (P) liquid component can be the same or different. Preferably, thepoly side (P) substance and the poly side (P) liquid component aredifferent. Preferably, the poly side (P) substance and the poly side (P)liquid component are the same. The iso side (I) liquid component and theiso side (I) substance can be the same or different. Preferably, the isoside (I) liquid component and the iso side (I) substance are the same.Preferably, the iso side (I) liquid component and the iso side (I)substance are different. (See FIG. 8).

Preferably, the chemical mechanical polishing layer prepared using themethod of the present invention can be interfaced with at least oneadditional layer (225) (e.g., a subpad) using a stack adhesive (210);wherein the stack adhesive (210) is interposed between the base surface(92) of the chemical mechanical polishing layer (90) and the additionallayer (225). The at least one additional layer preferably improvesconformance of the chemical mechanical polishing layer to the surface ofthe substrate being polished. Preferably, the stack adhesive (210) usedis an adhesive selected from the group consisting of pressure sensitiveadhesives, reactive hot melt adhesives, contact adhesives andcombinations thereof. More preferably, the stack adhesive used isselected from the group consisting of reactive hot melt adhesives andpressure sensitive adhesives. Most preferably, the stack adhesive usedis a reactive hot melt adhesive. (See FIG. 9).

Preferably, the chemical mechanical polishing pad (200) of the presentinvention is adapted to be interfaced with the platen of a polishingmachine. Preferably, the chemical mechanical polishing pad (200) isadapted to be interfaced with the platen using at least one of a vacuumand a pressure sensitive platen adhesive (230). Preferably, the chemicalmechanical polishing pad (200) is adapted to be interfaced with theplaten using a pressure sensitive platen adhesive (230). Preferably,when the chemical mechanical polishing pad of the present invention isoutfitted with a pressure sensitive platen adhesive (230), the chemicalmechanical polishing pad will also have a release layer (240) appliedover the pressure sensitive platen adhesive (230). (See, e.g., FIG. 9).

Preferably, the method of polishing a substrate of the presentinvention, comprises: providing the substrate; wherein the substrate isselected from at least one of a magnetic substrate, an optical substrateand a semiconductor substrate; providing a chemical mechanical polishingpad having a chemical mechanical polishing layer according to thepresent invention; creating dynamic contact between the polishingsurface of the chemical mechanical polishing layer and the substrate topolish a surface of the substrate; and, conditioning of the polishingsurface with an abrasive conditioner. More preferably, the method ofpolishing a substrate of the present invention, comprises: providing thesubstrate; wherein the substrate is a semiconductor substrate having aTEOS feature; providing a chemical mechanical polishing pad having achemical mechanical polishing layer according to the present invention;creating dynamic contact between the polishing surface of the chemicalmechanical polishing layer and the substrate to polish a surface of thesubstrate; wherein at least some of the TEOS is removed from thesubstrate; and, conditioning of the polishing surface with an abrasiveconditioner. Still more preferably, the method of polishing a substrateof the present invention, comprises: providing the substrate; whereinthe substrate is a semiconductor substrate having a TEOS feature;providing a chemical mechanical polishing pad having a chemicalmechanical polishing layer according to the present invention; providinga polishing medium; wherein the polishing medium comprises a colloidalsilica abrasive; dispensing the polishing medium onto the polishingsurface of the chemical mechanical polishing pad in proximity to aninterface between the chemical mechanical polishing pad and thesubstrate; wherein the polishing medium comes into contact with the TEOSfeature and the polishing surface; creating dynamic contact between thepolishing surface of the chemical mechanical polishing layer and thesubstrate to polish a surface of the substrate; wherein at least some ofthe TEOS is removed from the substrate; and, conditioning of thepolishing surface with an abrasive conditioner

Some embodiments of the present invention will now be described indetail in the following Examples.

COMPARATIVE EXAMPLE C1 Polishing Layer

A poly side (P) liquid component was provided, containing: 88.62 wt %high molecular weight polyether polyol (Voralux® HF 505 polyol availablefrom The Dow Chemical Company); 10.0 wt % monoethylene glycol; 1.23 wt %of a silicone surfactant (Tegostab® B8418 surfactant available fromEvonik); 0.05 wt % of a tin catalyst (Fomrez® UL-28 available fromMomentive); and, 0.10 wt % of a tertiary amine catalyst (Dabco® 33LVcatalyst available from Air Products, Inc.). An iso side (I) liquidcomponent was provided, containing: 100 wt % of a modifieddiphenylmethane diisocyanate (Isonate™ 181 MDI prepolymer available fromThe Dow Chemical Company.) A pressurized gas (dry air) was provided.

An axial mixing device was provided (a MicroLine 45 CSM available fromHennecke GmbH) having a (P) side liquid feed port, an (I) side liquidfeed port and four tangential pressurized gas feed ports. The poly side(P) liquid component and the iso side (I) liquid component were fed tothe axial mixing device through their respective feed ports with a (P)side charge pressure of 9,500 kPa, an (I) side charge pressure of 11,100kPa and at a weight ratio of (I)/(P) of 0.71 (giving a stoichiometricratio of reactive hydrogen groups to NCO groups of 0.95). Thepressurized gas was fed through the tangential pressurized gas feedports with a supply pressure of 830 kPa to give a combined liquidcomponent to gas mass flow rate ratio through the axial mixing device of4.5 to 1 to form a combination. The combination was discharged from theaxial mixing device toward a mold base having a negative of a groovepattern formed therein (a negative K7 type pattern of concentriccircular grooves) at a velocity of 254 m/sec to form a cake on the moldbase. The cake was allowed to cure for 16 hours at 100° C. The cake wasthen allowed to cool to room temperature before separating it from themold base. The bottom surface of the cake was machined flat on a latheto provide a polishing layer. The polishing layer was then mated to aSuba IV subpad using a hot melt adhesive to provide a chemicalmechanical polishing pad with a chemical mechanical polishing layerhaving a K7 type groove pattern (concentric circular grooves 20 milwide; 30 mil deep; 70 mil pitch).

EXAMPLE 1 Polishing Layer

A poly side (P) liquid component was provided, containing: 88.62 wt %high molecular weight polyether polyol (Voralux® HF 505 polyol availablefrom The Dow Chemical Company); 10.0 wt % monoethylene glycol; 1.23 wt %of a silicone surfactant (Tegostab® B8418 surfactant available fromEvonik); 0.05 wt % of a tin catalyst (Fomrez® UL-28 available fromMomentive); and, 0.10 wt % of a tertiary amine catalyst (Dabco 33LVcatalyst available from Air Products, Inc.). An additional liquidmaterial (Specflex™ NR 556 CO₂/aliphatic amine adduct available from TheDow Chemical Company) was added to the poly side (P) liquid component at3 parts per 100 parts poly side (P) liquid component by weight. An isoside (I) liquid component was provided, containing: 100 wt % of amodified diphenylmethane diisocyanate (Isonate™ 181 MDI prepolymeravailable from The Dow Chemical Company.) A pressurized gas (dry air)was provided.

An axial mixing device was provided (a MicroLine 45 CSM available fromHennecke GmbH) having a (P) side liquid feed port, an (I) side liquidfeed port and four tangential pressurized gas feed ports. The poly side(P) liquid component and the iso side (I) liquid component were fed tothe axial mixing device through their respective feed ports with a (P)side charge pressure of 8,600 kPa, an (I) side charge pressure of 13,100kPa and at a weight ratio of (I)/(P) of 0.83 (giving a stoichiometricratio of reactive hydrogen groups to NCO groups of 0.95). Thepressurized gas was fed through the tangential pressurized gas feed portwith a supply pressure of 830 kPa to give a combined liquid component togas mass flow rate ratio through the axial mixing device of 4.4 to 1 toform a combination. The combination was discharged from the axial mixingdevice toward a mold base having a negative of a groove pattern formedtherein (a negative K7 type pattern of concentric circular grooves) at avelocity of 254 m/sec to form a cake on the mold base. The cake wasallowed to cure for 16 hours at 100° C. The cake was then allowed tocool to room temperature before separating it from the mold base. Thebottom surface of the cake was machined flat on a lathe to provide apolishing layer. The polishing layer was then mated to a Suba IV subpadusing a hot melt adhesive to provide a chemical mechanical polishing padwith a chemical mechanical polishing layer having a K7 type groovepattern (concentric circular grooves 20 mil wide; 30 mil deep; 70 milpitch).

Polishing Layer Properties

The polishing layers from Comparative Example C1 and Example 1 wereanalyzed to determine their physical properties as reported in TABLE 3.Note that the density data reported were determined according to ASTMD1622; the Shore D hardness data reported were determined according toASTM D2240; and, the elongation to break data reported were determinedaccording to ASTM D412.

TABLE 3 Example Property Ex. C1 Ex. 1 Density (g/cm³) 0.66 0.57 Shore DHardness, @ 15 s 29 26 porosity (in vol %) 43 50 G′-40° C. (MPa) 11 11G″-40° C. (MPa) 1.1 1.3 G′-30° C./G′-90° C. 2.4 2.7 Tensile strength(MPa) 6.2 7.3 Elongation to break (%) 252 202 Tensile modulus (MPa) 15.428.3 Toughness (MPa) 11.0 10.7

COMPARATIVE EXAMPLE PC1 AND EXAMPLE P1 Chemical Mechanical PolishingRemoval Rate Experiments

Silicon dioxide removal rate polishing tests were performed using thechemical mechanical polishing pad prepared according to Example 1 andcompared with those obtained using the chemical mechanical polishing padprepared according to Comparative Example Cl. Specifically, the silicondioxide removal rate for each of the polishing pads is provided in TABLE4. The polishing removal rate experiments were performed on 200 mmblanket S15KTEN TEOS sheet wafers from Novellus Systems, Inc. An AppliedMaterials 200 mm Mirra® polisher was used. All polishing experimentswere performed with a down force of 20.7 kPa (3 psi), a slurry flow rateof 200 ml/min (Klebosol™ 1730 slurry available from Rohm and HaasElectronic Materials CMP Inc.), a table rotation speed of 93 rpm and acarrier rotation speed of 87 rpm. A Saesol 8031C diamond pad conditioner(commercially available from Saesol Diamond Ind. Co., Ltd.) was used tocondition the polishing pads. The polishing pads were each broken inwith the conditioner using a down force of 31.1 N for 30 minutes. Thepolishing pads were further conditioned 100% in situ during polishing at10 sweeps/min from 1.7 to 9.2 in from the center of the polishing padwith a down force of 31.1 N. The removal rates were determined bymeasuring the film thickness before and after polishing using aKLA-Tencor FX200 metrology tool using a 49 point spiral scan with a 3 mmedge exclusion. Each of the removal rate experiments were performedthree times. The average removal rate for the triplicate removal rateexperiments for each of the polishing pads is provided in TABLE 4.

TABLE 4 TEOS Chemical mechanical removal rate Ex # polishing pad (Å/min)PC1 Comparative Example C1 1596 P1 Example 1 2046

We claim:
 1. A chemical mechanical polishing pad, comprising: a chemicalmechanical polishing layer having a polishing surface, a base surfaceand an average polishing layer thickness, T_(P-avg), measured normal tothe polishing surface from the base surface to the polishing surface;wherein the chemical mechanical polishing layer is formed by combining apoly side (P) liquid component and an iso side (I) liquid component;wherein the poly side (P) liquid component comprises an amine-carbondioxide adduct; and, at least one of a (P) side polyol, a (P) sidepolyamine and a (P) side alcohol amine; wherein the iso side (I) liquidcomponent, comprising at least one (I) side polyfunctional isocyanate;wherein the chemical mechanical polishing layer has a porosity of ≧10vol %; wherein the chemical mechanical polishing layer has a Shore Dhardness of <40; and, wherein the polishing surface is adapted forpolishing a substrate.
 2. The chemical mechanical polishing pad of claim1, wherein the poly side (P) liquid component comprises: 1 to 5 wt % ofthe amine-carbon dioxide adduct; and, 25 to 95 wt % of the (P) sidepolyol; wherein the (P) side polyol is a high molecular weight polyetherpolyol; wherein the high molecular weight polyether polyol has a numberaverage molecular weight, M_(N), of 2,500 to 100,000 and an average of 4to 8 hydroxyl groups per molecule.
 3. The chemical mechanical polishingpad of claim 2, wherein the poly side (P) liquid component furthercomprises: 10 to 30 wt % of a low molecular weight polyol; wherein thelow molecular weight polyol has a number average molecular weight, MN,of ≦200.
 4. The method of claim 1, wherein the (I) side polyfunctionalisocyanate has an average of two reactive isocyanate groups permolecule.
 5. The method of claim 3, wherein the poly side (P) liquidcomponent further comprises: at least one of a catalyst and asurfactant.
 6. A method of making a chemical mechanical polishing layer,comprising: providing a poly side (P) liquid component, comprising anamine-carbon dioxide adduct; and, at least one of a (P) side polyol, a(P) side polyamine and a (P) side alcohol amine; providing a iso side(I) liquid component, comprising at least one at least one (I) sidepolyfunctional isocyanate; providing a pressurized gas; providing anaxial mixing device having an internal cylindrical chamber; wherein theinternal cylindrical chamber has a closed end, an open end, an axis ofsymmetry, at least one (P) side liquid feed port that opens into theinternal cylindrical chamber, at least one (I) side liquid feed portthat opens into the internal cylindrical chamber, and at least onetangential pressurized gas feed port that opens into the internalcylindrical chamber; wherein the closed end and the open end areperpendicular to the axis of symmetry; wherein the at least one (P) sideliquid feed port and the at least one (I) side liquid feed port arearranged along a circumference of the internal cylindrical chamberproximate the closed end; wherein the at least one tangentialpressurized gas feed port is arranged along the circumference of theinternal cylindrical chamber downstream of the at least one (P) sideliquid feed port and the at least one (I) side liquid feed port from theclosed end; wherein the poly side (P) liquid component is introducedinto the internal cylindrical chamber through the at least one (P) sideliquid feed port at a (P) side charge pressure of 6,895 to 27,600 kPa;wherein the iso side (I) liquid component is introduced into theinternal cylindrical chamber through the at least one (I) side liquidfeed port at an (I) side charge pressure of 6,895 to 27,600 kPa; whereina combined mass flow rate of the poly side (P) liquid component and theiso side (I) liquid component to the internal cylindrical chamber is 1to 500 g/s; wherein the poly side (P) liquid component, the iso side (I)liquid component and the pressurized gas are intermixed within theinternal cylindrical chamber to form a combination; wherein thepressurized gas is introduced into the internal cylindrical chamberthrough the at least one tangential pressurized gas feed port with asupply pressure of 150 to 1,500 kPa; wherein an inlet velocity into theinternal cylindrical chamber of the pressurized gas is 50 to 600 m/scalculated based on ideal gas conditions at 20° C. and 1 atm pressure;discharging the combination from the open end of the internalcylindrical chamber toward a target at a velocity of 5 to 1,000 m/sec;allowing the combination to solidify into a cake; and, deriving thechemical mechanical polishing layer from the cake, wherein the chemicalmechanical polishing layer has a porosity of ≧10 vol % and a polishingsurface adapted for polishing a substrate.
 7. The method of claim 6,further comprising: providing a poly side (P) substance, comprising atleast one of the (P) side polyol, the (P) side polyamine and the (P)side alcohol amine; providing a iso side (I) substance, comprising atleast one (I) side polyfunctional isocyanate; wherein the poly side (P)substance is introduced into the internal cylindrical chamber throughthe at least one (P) side liquid feed port at the (P) side chargepressure of 6,895 to 27,600 kPa; wherein the iso side (I) substance isintroduced into the internal cylindrical chamber through the at leastone (I) side liquid feed port at the (I) side charge pressure of 6,895to 27,600 kPa; wherein a combined mass flow rate of the poly side (P)substance and the iso side (I) substance to the internal cylindricalchamber is 1 to 500 g/s; wherein the poly side (P) substance, the isoside (I) side substance and the pressurized gas are intermixed withinthe internal cylindrical chamber to form a mixture; wherein thepressurized gas is introduced into the internal cylindrical chamberthrough the at least one tangential pressurized gas feed port with thesupply pressure of 150 to 1,500 kPa; wherein the inlet velocity into theinternal cylindrical chamber of the pressurized gas is 50 to 600 m/scalculated based on ideal gas conditions at 20° C. and 1 atm pressure;discharging the mixture from the open end of the internal cylindricalchamber toward a base surface of the chemical mechanical polishing layerat a velocity of 5 to 1,000 m/sec; allowing the mixture to solidify onthe base surface of the chemical mechanical polishing layer to form asubpad; wherein the subpad is integral with the chemical mechanicalpolishing layer; wherein the subpad has a subpad porosity that isdifferent from that of the chemical mechanical polishing layer.
 8. Amethod of polishing a substrate, comprising: providing the substrate;wherein the substrate is selected from at least one of a magneticsubstrate, an optical substrate and a semiconductor substrate; providinga chemical mechanical polishing pad comprising a chemical mechanicalpolishing layer according to claim 1; creating dynamic contact betweenthe polishing surface of the chemical mechanical polishing layer and thesubstrate to polish a surface of the substrate; and, conditioning of thepolishing surface with an abrasive conditioner.
 9. The method of claim8, wherein the semiconductor substrate has a TEOS feature; and, whereinat least some TEOS is removed from the substrate.
 10. The method ofclaim 9, further comprising: providing a polishing medium; wherein thepolishing medium comprises a colloidal silica abrasive; dispensing thepolishing medium onto the polishing surface of the chemical mechanicalpolishing pad in proximity to an interface between the chemicalmechanical polishing pad and the substrate; wherein the polishing mediumcomes into contact with the TEOS feature and the polishing surface.